Novel bifunctionalization-based microporous organic network material as well as preparation method and application thereof

Abstract

The invention relates to a novel bifunctionalization-based microporous organic network material as well as a preparation method and application thereof, and belongs to the technical field of microporous organic network materials. The invention aims to solve the technical problems of non-ideal adsorption performance, harsh preparation conditions, high energy consumption and poor pH applicability of the existing adsorbent. The preparation method of the novel bifunctional microporous organic network material comprises the following steps: dissolving a proper amount of cocatalyst cuprous iodide, a catalyst, reaction monomer rigid trialkyne and bifunctional aromatic trihalide in a mixed solvent, carrying out ultrasonic treatment, and carrying out magnetic stirring in an oil bath to obtain a head product; and washing the initial product, and carrying out vacuum drying to obtain the novel bifunctional microporous organic network material. The novel bifunctional microporous organic network material provided by the invention has relatively good hydrophilicity, and is beneficial to relatively good dispersion in an aqueous solution.

Description

Technical Field

[0001] The present application relates to the technical field of microporous organic network materials, and in particular to a novel dual-functionalized microporous organic network material and its preparation method and application. Background Art

[0002] In recent years, due to the rapid development of industrialization and urbanization, water pollution has become a serious global environmental problem. Organic dyes are widely used in various industries such as textiles, leather, paint, papermaking and printing, and are a major source of water pollution. Water-soluble dyes are toxic, stable organic compounds that can impair the photosynthetic capacity of aquatic plants and have a negative impact on the environment. In addition, through enrichment in the food chain, most dyes can cause dermatitis, allergies, gene mutations and cancer. On the other hand, antibiotics are widely used to treat human and animal diseases. As a major producer and user of antibiotics, my country produces and consumes a large amount of antibiotics every year. When these drugs are discharged into the environment, they may endanger the ecosystem and therefore have attracted widespread attention. Because many dyes and antibiotics have stable chemical structures (such as aromatic rings and azo groups), their removal from aqueous solutions is challenging.

[0003] Among numerous removal technologies, adsorption is considered the most effective and promising method for wastewater treatment due to its low cost, simple operation, and minimal secondary pollution. The key lies in the development of highly efficient adsorbents. Current adsorbents suffer from suboptimal adsorption performance, demanding preparation conditions, high energy consumption, and poor pH compatibility. A Chinese patent, publication number CN115845808 A, discloses a cellulose gel that efficiently adsorbs methylene blue. While the preparation method is relatively simple, it requires a high material-to-liquid ratio of 1 g:50 mL. A Chinese patent, publication number CN112316927 A, discloses the assembly of magnetic nanoparticles onto functionalized carbon nanotubes, achieving a methylene blue removal rate exceeding 95% within 20 minutes. However, the synthesis process requires nitrogen protection, placing strict demands on reaction conditions. A Chinese patent, publication number CN113277508 A, discloses high-surface-area activated carbon with high methylene blue adsorption efficiency, but requires activation at 600–900°C, resulting in high energy consumption. A Chinese patent, published under the number CN 116870879 A, discloses a metal oxoate combined with a MOF material, capable of achieving 99.69% adsorption of methylene blue in water at a pH of 5 within 2 minutes. However, the material synthesis process requires strict control of the pH to 1.7, as a pH change of 0.05 significantly impacts adsorption performance. Similar issues also exist in the removal of antibiotics. Therefore, developing adsorbent materials with high adsorption performance, simple and energy-efficient preparation methods, and a wide pH range of applicability is of great significance for the removal of organic pollutants. Summary of the Invention

[0004] In view of this, the present application provides a novel bifunctionalized microporous organic network material and its preparation method and application. The novel bifunctionalized microporous organic network material has good hydrophilicity, which is conducive to better dispersion in aqueous solution; at the same time, the material has a high specific surface area and bifunctional groups, provides more active adsorption sites, enriches the adsorption mechanism, quickly removes organic pollutants, and can effectively overcome the defects of the above-mentioned existing technologies.

[0005] The first aspect of the present application provides a preparation method based on a novel dual-functionalized microporous organic network material, comprising the following steps:

[0006] An appropriate amount of co-catalyst cuprous iodide, a catalyst, a reaction monomer rigid trialkyne and a bifunctional aromatic trihalide are dissolved in a mixed solvent, ultrasonically treated, and magnetically stirred in an oil bath to obtain a primary product; after washing the primary product, it is vacuum dried to obtain a novel bifunctionalized microporous organic network material.

[0007] The present application provides a method for rapidly removing organic pollutants based on a novel bifunctionalized microporous organic network material. The method is based on a novel bifunctionalized microporous organic network adsorption material, which is formed by coupling a tri-alkyne benzene series with a uniform structure and a trihalogen-substituted benzene series, and the aromatic halide has a bifunctional group. Different from the hydrophobic microporous organic network in the prior art CN117402324A and CN 108359079A, the novel bifunctionalized microporous organic network of the present application has good hydrophilicity, which is conducive to better dispersion in aqueous solution; at the same time, the material has a high specific surface area and bifunctional groups, providing more active adsorption sites and enriching the adsorption mechanism; combined with a novel integrated ultrasonic filtration device, the rapid removal of organic pollutants is achieved.

[0008] Preferably, the catalyst is one of bis(triphenylphosphine)palladium dichloride, 1,2-bis(diphenylphosphino)ethanepalladium dichloride, 1,3-bis(diphenylphosphino)propanepalladium dichloride, and 1,1'-bis(diphenylphosphino)ferrocenepalladium dichloride; and the mixed solvent is one of a mixed solution of triethylamine and toluene, a mixed solution of diethylamine and toluene, a mixed solution of dimethylformamide and toluene, and a mixed solution of ether and toluene.

[0009] Preferably, the ultrasonic time is 5 to 30 minutes.

[0010] Preferably, the molar ratio of the rigid trialkyne to the difunctional aromatic trihalide is 1:1.

[0011] Preferably, the amount of the co-catalyst cuprous iodide and the catalyst is 0.025 to 0.1 times the amount of the total amount of the reaction monomers.

[0012] Preferably, the oil bath temperature is 30-90° C., and the stirring time is 2-6 h.

[0013] Preferably, the vacuum drying temperature is 65-85°C.

[0014] The second aspect of the present application also provides a novel dual-functionalized microporous organic network material prepared by the above-mentioned method.

[0015] The third aspect of the present application also provides the application of the above-mentioned novel dual-functionalized microporous organic network material in removing organic pollutants.

[0016] The novel bifunctionalized microporous organic network material (1-400 mg) was added to the integrated ultrasonic filtration device from the feed port, and 25-1000 mL of a 1-100 mg / L dye or antibiotic solution with a pH of 5-11 was pumped in at an ultrasonic frequency of 50-600 W for 5-30 s. The mixed solution was pumped out to the filtration device, and the vacuum pump was turned on to complete the filtration, with a removal rate of more than 99.5%.

[0017] Compared with the prior art, this application has the following beneficial effects:

[0018] In response to the problems of current adsorbents with unsatisfactory adsorption performance, harsh preparation conditions, high energy consumption, and poor pH applicability, this application has developed a bifunctionalized microporous organic network material with high adsorption performance, which can effectively remove 99.5% of organic matter with 30 seconds of ultrasound. The higher specific surface area provides more adsorption sites, and the more functional groups enrich the adsorption mechanism. The bifunctional groups increase the hydrophilicity of the material, and the adsorption process does not require the addition of organic solvents, and it can be well dispersed in aqueous solution, making the adsorption process efficient and environmentally friendly. The preparation method is simple, with low energy consumption, and can be prepared by magnetic stirring at 90°C. It has a wide pH applicability range and has high adsorption performance in the pH range of 2-11. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to more clearly illustrate the technical solutions in the present application or the prior art, the following briefly introduces the drawings required for use in the description of the present application or the prior art. Obviously, the drawings described below are some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0020] Figure 1 Schematic diagram of the synthesis route of the novel dual-functionalized microporous organic network material prepared in Example 1;

[0021] Figure 2This is an infrared spectrum of the novel dual-functionalized microporous organic network material prepared in Example 1;

[0022] Figure 3 This is the XPS graph of the novel dual-functionalized microporous organic network material prepared in Example 1, wherein Figure 3 (a) is C1s, Figure 3 (b) is O1s;

[0023] Figure 4 This is a scanning electron microscope image of the novel dual-functionalized microporous organic network material prepared in Example 1;

[0024] Figure 5 This is the N2 adsorption analysis thermodynamic diagram based on the novel dual-functionalized microporous organic network material prepared in Example 1;

[0025] Figure 6 This is a pore size distribution diagram based on the novel dual-functionalized microporous organic network material prepared in Example 1;

[0026] Figure 7 This is the thermogravimetric image of the novel dual-functionalized microporous organic network material prepared in Example 1;

[0027] Figure 8 This is a contact angle diagram based on the novel dual-functionalized microporous organic network material prepared in Example 1;

[0028] Figure 9 This is a graph showing the adsorption performance of the novel dual-functionalized microporous organic network material prepared in Example 1 (a, b, c, and d represent methylene blue, azoarsenic, flumequine, and enrofloxacin, respectively);

[0029] Figure 10 This is a pH adaptability test chart based on the novel dual-functionalized microporous organic network material prepared in Example 1;

[0030] Figure 11 This is a schematic diagram of the structure of a new integrated ultrasonic filtration device.

[0031] Description of reference numerals:

[0032] 1. Wastewater bottle; 2. Pump; 3. Polytetrafluoroethylene container; 4. Liquid inlet; 5. Feeding port; 6. Liquid outlet; 7. Water outlet; 8. Transducer; 9. Ultrasonic power supply; 10. Filter device. DETAILED DESCRIPTION

[0033] To make the objectives, technical solutions, and advantages of this application more clear, the technical solutions of this application will be clearly and completely described below in conjunction with the accompanying drawings. Obviously, the embodiments described are only part of the embodiments of this application, not all of them. Based on the embodiments of this application, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of this application.

[0034] Unless otherwise specified, the experimental methods used in the examples of this application are all conventional methods.

[0035] In the following examples, unless otherwise specified, all raw materials can be purchased commercially or prepared by conventional methods.

[0036] Example 1

[0037] 0.048 mmol of bis(triphenylphosphine)palladium dichloride was weighed into a round-bottom flask. 0.048 mmol of CuI, 0.48 mmol of 3-hydroxy-2,4,6-triiodobenzoic acid, and 0.48 mmol of 1,3,5-triethynylbenzene were also weighed into the round-bottom flask. 30 mL of toluene and triethylamine were added, respectively, and the mixture was sonicated for 30 minutes. The round-bottom flask was transferred to a 90°C oil bath and stirred for 2 hours. The resulting product was washed four times with dichloromethane, four times with anhydrous ethanol, and twice with methanol. The product was then dried under vacuum at 65°C overnight to obtain a novel bifunctionalized microporous organic network material, designated BMON.

[0038] Example 2 (Changing the Ratio of Reactants)

[0039] 0.048 mmol of bis(triphenylphosphine)palladium dichloride was added to a round-bottom flask. 0.048 mmol of CuI, 0.72 mmol of 3-hydroxy-2,4,6-triiodobenzoic acid, and 0.48 mmol of 1,3,5-triethynylbenzene were also added to the flask. 30 mL of toluene and triethylamine were added, respectively, and the mixture was sonicated for 30 minutes. The flask was transferred to a 90°C oil bath and stirred for 2 hours. The resulting product was washed four times with dichloromethane, four times with anhydrous ethanol, and twice with methanol. The product was then dried in vacuo at 65°C overnight to obtain a novel bifunctionalized microporous organic network material, designated BMON-1.

[0040] Example 3 (Changing the catalyst ratio)

[0041] 0.024 mmol of bis(triphenylphosphine)palladium dichloride was added to a round-bottom flask. 0.024 mmol of CuI, 0.72 mmol of 3-hydroxy-2,4,6-triiodobenzoic acid, and 0.48 mmol of 1,3,5-triethynylbenzene were also added to the flask. 30 mL of toluene and triethylamine were added, respectively, and the mixture was sonicated for 30 minutes. The flask was transferred to a 90°C oil bath and stirred for 2 hours. The resulting product was washed four times with dichloromethane, four times with anhydrous ethanol, and twice with methanol. The product was then dried under vacuum at 65°C overnight to obtain a novel bifunctionalized microporous organic network material, designated BMON-2.

[0042] Example 4 (Changing Reaction Time)

[0043] 0.048 mmol of bis(triphenylphosphine)palladium dichloride was added to a round-bottom flask. 0.048 mmol of CuI, 0.48 mmol of 3-hydroxy-2,4,6-triiodobenzoic acid, and 0.48 mmol of 1,3,5-triethynylbenzene were also added to the flask. 30 mL of toluene and triethylamine were added, respectively, and the mixture was sonicated for 30 minutes. The flask was transferred to a 90°C oil bath and stirred for 6 hours. The resulting product was washed four times with dichloromethane, four times with anhydrous ethanol, and twice with methanol. The product was dried in vacuo at 65°C overnight to obtain a novel bifunctionalized microporous organic network material, designated BMON-3.

[0044] Comparative Example 1

[0045] According to Example 1 of CN 117402324A, a microporous organic network material was prepared, and its water contact angle was 147°, indicating that MONs are highly hydrophobic.

[0046] According to Example 1 of CN 108359079A, a microporous organic network material was prepared, and its contact angle was 140.7°, that is, MONs has strong hydrophobicity.

[0047] Test Case

[0048] In order to make the removal process more simple and efficient, the present application provides an integrated ultrasonic filtration device. Figure 11 As shown, an acid- and alkali-resistant polytetrafluoroethylene container 3 is embedded in the ultrasonic system to accommodate waste liquids of various properties. The polytetrafluoroethylene container 3 has a liquid inlet 4, a feed port 5, a liquid outlet 6, and a water outlet 7. Two transducers 8 are located below the container, both connected to an ultrasonic power supply 9. The feed port 5 is used to add a bifunctionalized microporous organic network adsorption material. A constant-pressure pump 2 is used to transfer the waste liquid from a wastewater bottle 1 to the polytetrafluoroethylene container 3. Ultrasound allows the material to fully contact the waste liquid, achieving efficient removal of organic pollutants. Pump 2 then outputs the mixed liquid from the removal system to a filtration device 10, achieving automated, integrated removal and filtration.

[0049] 8-10 mg of the novel bifunctionalized microporous organic network material prepared in Example 1 was added to the integrated ultrasonic filtration device from the feed port 5, and 100 mL of a 20 mg / L dye or antibiotic solution with a pH of 11 was pumped in. The mixture was ultrasonically treated at an ultrasonic frequency of 300 W for 30 seconds, and the mixture was pumped out to the filtration device 10 for filtration. This achieved efficient removal of the antibiotics, with a removal rate of 99.5%.

[0050] like Figure 1 Shown is a synthesis diagram of a bifunctionalized microporous organic network material. This material is formed by coupling a structurally uniform triacetylenic benzene series with a trihalogen-substituted benzene series, with the aromatic halide bearing bifunctional groups. The novel bifunctionalized microporous organic network described in this application exhibits good hydrophilicity, facilitating good dispersion in aqueous solutions. Furthermore, the material possesses a high specific surface area and bifunctional groups, providing a greater number of active adsorption sites and enriching the adsorption mechanism. Combined with a novel integrated ultrasonic filtration device, it achieves rapid removal of organic pollutants.

[0051] like Figure 2 As shown, the FT-IR absorption band is at 3431.35 cm -1 The appearance of α at 2207.01 cm is attributed to the stretching vibration of hydroxyl groups on the surface of BMON. -1 The absorption peak appears, which is the stretching peak of the triple bond disubstituted, indicating the successful coupling of the reaction monomer. -1 The peak at 1577.86cm is the typical stretching vibration of carbonyl. -1 The peaks at 1381.42, 1284.84 and 879.30 cm-1 are attributed to the aromatic ring skeleton vibration in BMON. -1 It corresponds to the in-plane bending of the OH group in the phenolic hydroxyl group of the benzene ring, the stretching of the CO group, and the bending vibration of the CH group on the aromatic ring.

[0052] like Figure 3 As shown, Figure 3 (a) is the C1s peak of BMON, which can be divided into five main peaks. The peaks at 284.6, 285.58, 286.80, 288.49, 290.08 and 291.97 eV correspond to C=C / CC, C≡C, C-OH, C=O, OC=O and π→π* bonds, respectively. Figure 3 (b) is O1s, which has three forms. The peaks at 531.63, 532.54 and 533.56 eV correspond to OH, C-OH and C=O.

[0053] like Figure 4 As shown, BMON is spherical with a diameter of approximately 450 nm.

[0054] like Figure 5 and Figure 6As shown, the Brunauer-Emmett-Teller (BET) specific surface area of BMON is 572 m 2 g -1 The shape of the pores conforms to the type I isotherm. The pore size distribution is between 0-2nm, and the most probable pore size is 0.73nm, which belongs to the microporous structure.

[0055] like Figure 7 As shown in Figure 3, the TGA curve shows that BMON remains stable up to 300°C, indicating that the material has good thermal stability.

[0056] like Figure 8 As shown in the figure, the water contact angle of BMON is 45°, indicating that BMONs have good hydrophilicity, which is conducive to the dispersion of BMON in aqueous solution and better adsorption of methylene blue.

[0057] like Figure 9 As shown in the figure, the BMON of the present application has a removal rate of more than 99.5% for 20 mg / L methylene blue, azoarsenic, flumequine, and enrofloxacin within 30 seconds. This performance is attributed to the high specific surface area of the material (572 m 2 / g) and the hydrogen bonding effect of the bifunctional groups combined with ultrasound-assisted mass transfer achieve efficient adsorption.

[0058] like Figure 10 As shown, the bifunctionalized BMON of the present application has a wide pH adaptability and has a high removal rate in the range of 2 to 12. When the pH is greater than 2 and less than 5, the removal rate is over 95%; when the pH is greater than 6, the removal rate is over 99.5%.

[0059] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some or all of the technical features therein. These modifications or replacements do not deviate the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A preparation method based on a novel dual-functionalized microporous organic network material, characterized in that: The following steps are involved: An appropriate amount of co-catalyst cuprous iodide, a catalyst, a reaction monomer rigid trialkyne and a bifunctional aromatic trihalide are dissolved in a mixed solvent, ultrasonically treated, and magnetically stirred in an oil bath to obtain a primary product; after washing the primary product, it is vacuum dried to obtain a novel bifunctionalized microporous organic network material.

2. The preparation method based on the novel dual-functionalized microporous organic network material according to claim 1, characterized in that: The catalyst is one of bis(triphenylphosphine)palladium dichloride, 1,2-bis(diphenylphosphino)ethanepalladium dichloride, 1,3-bis(diphenylphosphino)propanepalladium dichloride, and 1,1'-bis(diphenylphosphino)ferrocenepalladium dichloride; and the mixed solvent is one of a mixed solution of triethylamine and toluene, a mixed solution of diethylamine and toluene, a mixed solution of dimethylformamide and toluene, and a mixed solution of ether and toluene.

3. The preparation method based on the novel dual-functionalized microporous organic network material according to claim 1, characterized in that: The ultrasonic time is 5 to 30 minutes.

4. The preparation method based on the novel dual-functionalized microporous organic network material according to claim 1, characterized in that: The molar ratio of the rigid trialkyne to the bifunctional aromatic trihalide is 1:

1.

5. The preparation method based on the novel dual-functionalized microporous organic network material according to claim 1, characterized in that: The usage of the co-catalyst cuprous iodide and the catalyst is 0.025 to 0.1 times of the total amount of the reaction monomers.

6. The preparation method based on the novel dual-functionalized microporous organic network material according to claim 1, characterized in that: The oil bath temperature is 30-90° C., and the stirring time is 2-6 hours.

7. The preparation method based on the novel dual-functionalized microporous organic network material according to claim 1, characterized in that: The vacuum drying temperature is 65-85°C.

8. A novel dual-functionalized microporous organic network material, characterized in that: A novel double-functionalized microporous organic network material prepared by the method described in any one of claims 1 to 7.

9. Use of the novel dual-functionalized microporous organic network material according to claim 8 in removing organic pollutants.

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